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Role of grain-to-grain contacts on profiles of retained colloids in porous media in the presence of an energy barrier to deposition.

Deposition of 36-microm gold-coated hollow microspheres in two porous media (glass beads and quartz sand, 710-850 microm) was examined using X-ray microtomography (XMT) in the presence of an energy barrier to deposition under fluid velocity conditions representative of engineered filtration systems. XMT allowed examination of the deposition at different locations at the grain surfaces (deposition at grain-to-grain contacts versus single-contact deposition). We demonstrate that in the presence of an energy barrier to deposition, grain-to-grain contacts strongly influence colloid deposition and the spatial distribution of retained colloids in porous media. This result contrasts drastically with observations in the absence of an energy barrier to deposition, where consistency with filtration theory was observed. In the presence of an energy barrier, colloids were dominantly retained at grain-to-grain contacts, and the concentration of retained particles varied nonmonotonically with transport distance. It is proposed that the nonmonotonic profiles resulted from translation of surface-associated microspheres and subsequent immobilization at grain-to-grain contacts. This hypothesis is demonstrated using a conceptual model. The mutability and sensitivity of retained profiles to system conditions (from hyper-exponential to nonmonotonic) may reflect the interplay of different deposition mechanisms under different conditions.

Colloids↗

A non-perturbing scheme for the mineralogical characterization and quantification of inorganic colloids in natural waters.

Although the role played by inorganic colloids in natural waters depends on their composition as well as on their size, the characterization of submicron particles has rarely gone beyond describing the morphology and identifying some of the most abundant particles. The process of quantification has been hampered by a lack of suitable analytical methods. This study demonstrates that it is possible to identify and quantify inorganic particles in the colloidal size range by applying a straightforward methodology based on a well-proved, quantitative, and nonperturbing method of sample preparation (direct centrifugation of the samples on transmission electron microscopy grids) in conjunction with particle analysis using widely available techniques: transmission electron microscopy, energy dispersive X-ray spectroscopy (EDS), and selected area electron diffraction (SAED). The method has successfully been applied to six water samples from basins of contrasting geological characteristics. The method has the advantage of minimizing sample modifications by allowing on site sample preparation, using standard equipment, and it is not particularly time-consuming. Notably, the combination of EDS and SAED information makes it possible to characterize and quantify the most abundant components of the colloidal pool in the majority of the aquatic systems: the different types of aluminosilicates.

Colloids↗

Stable colloidal dispersions of C60 fullerenes in water: evidence for genotoxicity.

Stable aqueous suspensions of colloidal C60 fullerenes free of toxic organic solvents were prepared by two methods: ethanol to water solvent exchange (EthOH/nC60 suspensions) and extended mixing in water (aqu/nC60 suspensions). The extended mixing method resulted in the formation of larger (dp approximately 178 nm) and less negatively charged (zeta approximately -13.5 mV) nC60 colloids than nC60 prepared by ethanol to water solvent exchange (dp approximately 122 nm, zeta approximately -31.6 mV). Genotoxicity of these suspensions was evaluated with respect to human lymphocytes using single-cell gel electrophoresis assay (Comet assay). The assay demonstrated genotoxicity for both types of suspensions with a strong correlation between the genotoxic response and nC60 concentration, and with genotoxicity observed at concentrations as low as 2.2 microg/L for aqu/nC60 and 4.2 microg/L for EtOH/nC60. The Olive tail moments (OTM) for these two concentrations were 1.54 +/- 0.24 and 1.34 +/- 0.07, respectively, which in comparison to the negative control OTM of 0.98 +/- 0.17 is statistically different with a p value of at least 0.05. Aqu/nC60 suspensions elicited higher genotoxic response than EthOH/nC60 for the same nC60 concentration. The results represent the first genotoxicity data for colloidal fullerenes produced by simple mixing in water.

Colloids↗

Epi-fluorescence imaging of colloid transport in porous media at decimeter scales.

A noninvasive epi-fluorescence imaging technique was developed for real-time observation of colloid transport in porous media at decimeter scales. Fluorescent latex microspheres and translucent quartz sand were used as a model colloid-porous medium system. Various calibrations were performed for accurate conversion of fluorescence intensities to microsphere concentrations. Fluorescence intensities were found to linearly increase with microsphere concentrations (5 x 10(5)-5 x 10(8) spheres/mL in saturated sand) and with camera exposure time. Fluorescence intensities also increased with sand thickness (saturated with microsphere solution), indicating that the fluorescence signals detected by the imaging system were integrated signals from the entire thickness (10 mm) of the sand. A set of microsphere transport experiments was conducted to demonstrate the versatility of the imaging system. Excellent mass recoveries (93-103%) were achieved in all transport experiments, demonstrating the robustness of the imaging system for quantitative study of colloid transport. The system allowed the change of flow velocity, ionic strength, and flow direction within one transport experiment and the real-time, quantitative monitoring of the movement of microspheres in packed sand, greatly reducing the time and effort needed for similar work with traditional column experiments.

Colloids↗

Self-assembly of spherical colloids into helical chains with well-controlled handedness.

Physical constraint and capillary force have been combined to provide a generic approach to assemble achiral building blocks such as monodisperse spherical colloids into helical mesostructures. The key component of this process is an array of V-shaped grooves anisotropically etched in the surface of a Si(100) wafer. The structural arrangement among the spherical colloids is determined by the ratio between the width of the V-grooves and the diameter of the colloids. Double-layered structures with a helical morphology will be formed when this ratio falls between 2.70 and 2.85. The exact handedness of these helical structures could be controlled by varying the relative orientation of capillary force with respect to the longitudinal axis of the spirals. The processing of an achiral material into helical mesostructures having well-controlled handedness should allow us to explore new properties that this material otherwise does not exhibit. The self-assembly process may also provide valuable insights to improve our understanding on the mechanism(s) by which pure enantiomers with a particular sense of rotation evolved in nature.

Colloids↗

Fabrication of colloidal crystals with tubular-like packings.

Methods are reported for the fabrication of colloidal crystal wires with tubular packings. Both free and silica-encased wires have been prepared. Porous silicon membranes are infiltrated with silica spheres, treated with silane, and annealed. After removal of the silicon template, short annealing times were found to result in colloidal crystal wires with varied packing geometries, while repeated annealing cycles produced a thin translucent silica sheath around the wires. Packing in the wires varies with the channel diameter of the Si membrane. The channels used in this study typically produce colloidal crystal wires with six strands, though wires with four to seven strands have been observed. Both chiral and achiral packings are also possible.

Biocompatible Materials↗

Amorphous Se: a new platform for synthesizing superparamagnetic colloids with controllable surfaces.

We have successfully incorporated iron oxide nanoparticles into monodispersed amorphous selenium (a-Se) colloids by regulating the reaction temperature during the synthesis of a-Se. The surfaces of these a-Se colloids could be coated with conformal and smooth shells made of Pt and SiO2. The Se cores could then be removed by etching with hydrazine. The spherical morphology and superparamagnetism were maintained in all these synthetic steps. The presence of Pt and SiO2 on the outer surfaces of these colloidal particles allows one to control their surface functionalities through the formation of alkanethiolate and siloxane monolayers, respectively.

Colloids↗

Swelling-based method for preparing stable, functionalized polymer colloids.

We describe a swelling-based method to prepare sterically stabilized polymer colloids with different functional groups or biomolecules attached to their surface. It should be applicable to a variety of polymeric colloids, including magnetic particles, fluorescent particles, polystyrene particles, PMMA particles, and so forth. The resulting particles are more stable in the presence of monovalent and divalent salt than existing functionalized colloids, even in the absence of any surfactant or protein blocker. While we use a PEG polymer brush here, the method should enable the use of a variety of polymer chemistries and molecular weights.

Colloids↗

Laser photolysis of silver colloid prepared by citric acid reduction method.

By irradiating a silver colloid, prepared via the citric reduction method, using the second harmonic of a Nd:YAG laser, lambda = 532 nm, with laser fluence more than about 0.2 J/cm(2), we prepared a colloid consisting of small spherical silver nanoparticles with d(p) = 8 nm. The process of particle formation can be divided into three steps. First, large particles that existed in the initial colloid evaporate fully, producing a large amount of silver atoms. Next, primary particles with d(p) = 2-4 nm are formed in mini plumes. Finally, these primary particles grow up to 8 nm, as silver atoms diffuse to them through water.

Citric Acid↗

Experimental phase diagram of symmetric binary colloidal mixtures with opposite charges.

The phase behavior of equimolar mixtures of oppositely charged colloidal systems with similar absolute charges is studied experimentally as a function of the salt concentration in the system and the colloid volume fraction. As the salt concentration increases, fluids of irreversible clusters, gels, liquid-gas coexistence, and finally, homogeneous fluids, are observed. Previous simulations of similar mixtures of Derjaguin-Landau-Verwey-Overbeek (DLVO) particles indeed showed the transition from homogeneous fluids to liquid-gas separation, but also predicted a reentrant fluid phase at low salt concentrations, which is not found in the experiments. Possibly, the fluid of clusters could be caused by a nonergodicity transition responsible for the gel phase in the reentrant fluid phase. Liquid-gas separation takes a delay time after the sample is prepared, whereas gels collapse from the beginning. The density of the liquid in coexistence with a vapor phase depends linearly on the overall colloid density of the system. The vapor, on the other hand, is comprised of equilibrium clusters, as expected from the simulations.

Colloids↗

Structural properties of nonionic cyclodextrin colloids in water.

The amphiphilic character in water of a novel class of chemically modified cyclodextrins has been investigated by means of small-angle X-ray scattering and light scattering. The introduction ofhydrophilic oligo(ethylene glycol) onto the secondary side of heptakis[6-alkylthio-6-deoxy-2-oligo(ethylene glycol)]-beta-cyclodextrins produces an enhanced water solubility of these molecules. Shape and dimensions of the generated micellar aggregates, analyzed in terms of a suitable core-shell model, remain stable in the wide concentration range explored. The highly associative behavior of these macromolecules is evidenced by the very low value of the critical micelle concentration (cmc), which is about 2 orders of magnitude smaller than the cmc usually obtained for traditional surfactant. Despite the complex geometry of this novel macromolecule, shape and dimensions of generated micellar aggregates can be properly described according to the thermodynamic approaches generally used for amphiphilic molecules and block copolymers. Results show how the modulation of hydrophobic and hydrophilic components sensitively influence the structural features of the generated aggregates thus offering the possibility to control molecular organization in a manner similar to that for traditional colloids. For all the classes of the investigated systems, the small micelles have been found in equilibrium with polydisperse large aggregates of entangled micelles. These novel nonionic colloidal systems combine inclusion and transport properties of host macrocycles, such as cyclodextrin, together with the increased stability of colloidal aggregates, and may be of interest for their potential application as innovative drug delivery systems.

Circular Dichroism↗

Silver-colloid-nucleated cytochrome c superstructures encapsulated in silica nanoarchitectures.

We recently discovered that self-organized superstructures of the heme protein cytochrome c (cyt. c) are nucleated in buffer by gold nanoparticles. The protein molecules within the superstructure survive both silica sol-gel encapsulation and drying from supercritical carbon dioxide to form air-filled biocomposite aerogels that exhibit gas-phase binding activity for nitric oxide. In this investigation, we report that viable proteins are present in biocomposite aerogels when the nucleating metal nanoparticle is silver rather than gold. Silver colloids were synthesized via reduction of an aqueous solution of Ag+ using either citrate or borohydride reductants. As determined by transmission electron microscopy and UV-visible absorption spectroscopy, the silver nanoparticles vary in size and shape depending on the synthetic route, which affects the fraction of cyt. c that survives the processing necessary to form a biocomposite aerogel. Silver colloids synthesized via the citrate preparation are polydisperse, with sizes ranging from 1 to 100 nm, and lead to low cyt. c viability in the dried bioaerogels (approximately 15%). Protein superstructures nucleated at approximately 10-nm Ag colloids prepared via the borohydride route, including citrate stabilization of the borohydride-reduced metal, retain significant protein viability within the bioaerogels (approximately 45%).

Chemical Phenomena↗

Nonlinear optical probe of biopolymer adsorption on colloidal particle surface: poly-L-lysine on polystyrene sulfate microspheres.

A nonlinear optical technique--second harmonic generation (SHG)--has been applied to characterize the adsorption of poly-L-lysine on micrometer size polystyrene particles, whose surface is covered with negatively charged sulfonate groups, in aqueous solutions. Adsorption behavior of the biopolymer with two chain lengths (14 and 75 amino acid units; PL14 and PL75) has been examined. Centrifugation experiments were also performed to support the adsorption measurements made using SHG. The adsorption free energies of the two polymers PL75 and PL14 are determined as -16.57 and -14.40 kcal/mol, respectively. The small difference in the adsorption free energies of the two chain lengths, however, leads to dramatic difference in the concentration needed for saturated surface coverage: nearly 50 times higher concentration is needed for the smaller polymer. Under acidic colloidal conditions, polylysine is found to adsorb in a relatively flat conformation on the surface. The surface area that each polylysine molecule occupies is nearly 1 order of magnitude larger than the size of the molecule in its extended form. The low adsorption density is likely a result from Coulombic repulsion between the positive charges on the amino acid units of PL. The measurements demonstrate the utility of SHG as an efficient and sensitive experimental approach for measuring adsorption characteristics of bio/macromolecules on colloidal particles and define surface and colloidal conditions for achieving maximum surface coverage of a widely used biopolymer.

Adsorption↗

Formation and properties of positively charged colloids based on polyelectrolyte complexes of biopolymers.

Formation of colloids based on polyelectrolyte complexes (PECs) was mainly studied with synthetic polyelectrolytes. In this study, we describe the elaboration of positively charged PEC particles at a submicrometer level obtained by the complexation between two charged polysaccharides, chitosan as polycation and dextran sulfate (DS) as polyanion. The complexes were elaborated by dropwise addition of default amounts of DS to excess chitosan. Quasi-elastic light scattering was used to investigate in detail the influence of the characteristics of components (chain length, degree of acetylation) and parameters linked to the reaction of complexation (molar mixing ratio, ionic strength, concentration in polymer) on the sizes and polydispersity of colloids. Chain length of chitosan is the major parameter affecting the dimensions of the complexes, high molar mass chitosans leading to the largest particles. Variations of hydrodynamic diameters of PECs with the molar mass of chitosan are consistent with a mechanism of particle formation through the segregation of the neutral and then hydrophobic blocks of the polyelectrolyte complexed segments. Resulting particles display probably a structure constituted by a neutral core surrounded by a chitosan shell ensuring the colloidal stabilization. Such a structure was evidenced by measurements of electrophoretic mobilities revealing that the positive charge of particles was decreasing with pH, in relation with the neutralization of excess glucosamine hydrochloride moieties.

Acetylation↗

Aggregation-fragmentation in a model of DNA-mediated colloidal assembly.

We present results from an off-lattice Monte Carlo simulation of DNA-mediated colloidal assembly. In this simulation, the aggregation-fragmentation of a binary mixture of DNA-coated colloidal particles is studied through a simplified model of base-pair hybridization. Bonding between monomers is modeled as a simple temperature-sensitive A/B-type interaction, where type A and B monomers can bond to only the opposite type (no A/A or B/B attachments are allowed). The actual chemistry of base-pair hybridization is not included in the model. The morphological structures of the clusters formed as well as the kinetics of growth are analyzed in our 2D simulations. The fractal dimension and kinetic growth exponents for clusters formed near the DNA "melting" temperature agree with those seen previously for 2D diffusion-limited cluster aggregation (DLCA) models. The clusters appear more compact, exhibiting signs of local order at intermediate temperature values. At higher temperatures, the formation of large clusters is not favorable under the action of temperature-dependent fragmentation, and the system eventually reaches a steady state as a collection of small aggregates. The temperature profile for this dissolution of the colloidal assembly is sharp, indicating that the selective hybridization process provides a highly sensitive measurement tool. At high temperatures, we analyze the steady-state behavior of the average cluster size in terms of an aggregation-fragmentation model.

Algorithms↗

Size selective assembly of colloidal particles on a template by directed self-assembly technique.

We report a simple and effective approach to organize micron- and submicron-sized particles in a size selective manner. This approach utilizes the template assisted directed self-assembly technique. A topographically patterned photoresist surface is fabricated and used to create an ordered array of colloidal particles from their aqueous suspensions. Assembly of particles on this template is then achieved by using a conventional spin coating technique. Feasibility of this technique to form a large area of patterned particle assemblies has been investigated. To arrange the particles on the template, the physical confinement offered by the surface topography must overcome a joint effect of centrifugal force and the hydrophobic nature of the photoresist surface. This concept has been extended to the size selective sorting of colloidal particles. The capability of this technique for sorting and organizing colloidal particles of a particular diameter from a mixture of microspheres is demonstrated.

Colloids↗

Microfluidic assembly of homogeneous and Janus colloid-filled hydrogel granules.

The microfluidic assembly of colloid-filled hydrogel granules of varying shape and composition is described. First, drops are formed by shearing a concentrated colloidal microsphere-acrylamide suspension in a continuous oil phase using a sheath-flow device. Both homogeneous and Janus (hemispherically distinct) spheres and disks are produced by confining the assembled drops in microchannels of varying geometry. Next, photopolymerization is carried out shortly after drop breakup to preserve their morphology. Representative wet and dried granules are characterized using fluorescence and scanning electron microscopy, respectively. Our approach offers a facile route for assembling colloid-filled hydrogel granules with controlled shape and composition.

Colloids↗

High resolution size determination of 20 nm colloidal gold particles by SedFFF.

PURPOSE: Assessment of lower size limit of Sedimentation Field-Flow Fractionation (SedFFF), specifically to evaluate if the method is suitable to determine the size and size distribution of 20 nm colloidal gold particles with high resolution. METHODS: Sedimentation Field-Flow Fractionation was used to determine the size of the colloidal particles. Due to the high density of gold it was possible to extend the lower size limit of SedFFF well below 20 nm. The size distribution of a gold colloid was obtained from the peak broadening caused by the polydispersity of the sample. The peak broadening due to instrumental imperfections was determined. For comparison purpose the particles were also sized using SEM and PCS. RESULTS: The mean diameter of the particles was determined to be (20.87+/-0.05) nm, the standard deviation in size being 1.04 nm (about 5%). SEM could confirm that the particles are about 20 nm in diameter. A sizing with PCS was not possible. The particles have a strong tendency to aggregate and PCS yields a diameter that is much too large. CONCLUSIONS: At optimized analytical parameters Sedimentation Field-Flow Fractionation is an effective method to measure the size of gold particles as small as 15 nm with an accuracy of about 0.1 nm. The polydispersity of the sample can easily be determined.

Chemical Fractionation↗